DE2035175B2 - PROCESS FOR THE RECOVERY OF WASTE, WASTE PARTS AND / OR DISPOSAL MATERIALS FROM POLYADDUCTS MANUFACTURED BY THE ISOCYANATE POLYADDITION PROCESS - Google Patents

Description

Far-reaching change in temperature control at - S -, - S - R - S - or - SO ₂ -. Examples

the production of some polyurethanes can be achieved. such connections could the German interpretative

The freezing point of 4,4'-diisocyanatodiscript 1091324 can be found in this way. Farther

phenyhnethane at 38 ^ C. A solution consisting of suitable are dimers or trimers of isocyanates

this diisocyanate and a cellular polyurethane 5 and diisocyanates or polymeric diisocyanates of

elastomers made from hydroxyl polyester, 1,5-naphthylene general formulas (RNGY) ₃ ; or [R (NCY) ₁ Ij ,, in

In contrast, dusocyanate and water are at room temperatures χ and y an integer from 2 upwards.

ture liquid and can thus be conveyed much more easily and the residues R and Y the

can be modified and dosed. Have given importance in further processing.

From a procedural point of view, this represents a major io. Of course, the aforementioned

Advantage. Polyisocyanates were used alone or in a mixture

As can be seen from the above, z. B. in the form of a mixture consisting of

is, the known recovery processes are 4,4'-diphenylmethane diisocyanate and 1,5-naphthylene-

mainly geared towards the waste of a use dusocyanate.

15 to the at least two active hydrogen atoms, i.e. organic compounds containing elastic hot foam waste belong to pillow fillings, rigid foam waste organic compounds whose active hydrogen is fillers for lightweight concrete and thermoplastic abatoms according to Zerewitinoffmit Grignard reagent cases used as additives to frichgranules. By reacting with the formation of methane, for example this type of waste recycling, the actual 20 ones that _{do not contain OH, - COOH, NH 2} - and / or material properties of the polyadducts entirely from SH groups. For example, belong to the used. In other words, the wastes in polyhydroxy compounds all short- and long-chain in their respective form of use represent a relatively worthless alcohol with at least two hydroxyl groups and a product 60 and 10,000.
The above-mentioned organic compounds containing active hydrogen atoms and waste, scrap parts and / or old materials can be elegantly processed into new valuable products, either alone or in combination with each other, which have the properties 3 ″ produced by the isocyanate polyaddition process has been specifically used according to the isocyanate polyaddition process.

Products correspond, for example, with the polyurethane waste to which the should be borrowed, cellular waste in massive products, process according to the invention particularly relates, dimensional Waste in cellular products, not thermoplastics, contributes to the molar ratio of total hydroxyl see waste in thermoplastics and thermoplastics from total isocyanate 1: (0.7 to 1.4) in the process to convert cases into non-thermoplastics. 35 of the isocyanate polyaddition process.

The subject matter of the invention is therefore a process from the waste, scrap parts and / or waste for the recycling of waste, scrap parts and / or materials are recycled according to the invention from polyadducts, which are preferably recycled after the process:
Known isocyanate polyaddition processes by reaction of organic polyisocyanates or polyiso- 40 ^a > cast, sprayed, centrifugally cast, thermothioeyanates with organic, at least two active plastic processing routes or compounds containing hydrogen atoms in the rolling process in the risk of massive or cellular polyurethanes in the presence of conventional chain extenders, catalysts, beelastomers in different hardness setting accelerators and other common additives, whereby the solid qualities have been set between hardnesses, which is characterized by having 45, 15 Shore A and 60 Shore D; that the waste consisting of the polyadducts ^b) flexible to semi-rigid polyurethane foam scrap parts and / or waste materials in 4,4 '-, 2,4'- substances with a specific weight between 0.1 and / or 2,2'-diphenylmethane diisocyanate or one and 0.8;

Mixture of isomers dissolves. ^c ) Granules of thermoplastically processable compounds The following compounds can have served 50 polyurethane elastomers in the most varied as starting components for the production of the poly, quality and hardness settings between adducts, which as waste, rejects ^{60 Shore A and 60 Shore D}
and / or old materials are to be recycled. According to the process according to the invention, in addition to the appropriately usable organic waste, rejects and / or old-fashioned polyisocaynates and polyisothiocyanates, in addition to those of the general formula R (NCY) _x , in the molecule, they can be used required constituents and reaction x means 2 or more, Y oxygen or sulfur aids additionally contain other admixtures, and R represents an alkylene radical, substituted such as fillers, stabilizers, surface-active substances, alkylene radical, arylene radical, substituted arylene radical, paints, pigments, lubricants, Heat exchangers, hydrocarbon or substituted hydrocarbon plasticizers, swelling agents, lubricants, antistatic agents, substance residues with one or more aryl-NCY bonds, bacteriostats, fungistats, flame-retardant compounds or one or more alkyl-NCY bonds and the like suggest, or which are blended with polymers a carbon hydrogen or substituted carbon on a different chemical basis, for example with a polyhydrogen radical with a large number of aryl-NCY or vinyl chloride or ABS polymers (acrylonitrile, buta-alkyl-NCY bonds. R can still serve for 65, styrene). Furthermore, you can stand after the residues of the invention, such. B. - R - Z - R - residues, whereby according to the method the waste, rejects and / Z can be any divalent residue, such as or waste materials in filled, pigmented or cellular - O -, - O - R - O -, - CO -, - CO ₂ -, transform products when you use the

5 6

solution according to the invention the corresponding diisocyanate, which has previously heated to 150 ⁰ C to aggregate the starting components by mutual leibt After a solution for 15 minutes at 150 ⁰ C to obtain complete solution of the waste.

The economic importance of the invention The solution obtained, which is at room temperature

The method lies in its simplicity, which remains liquid, is processed further into a cellular polyurethane elasto with no noteworthy new investments for its diameter according to the following recipe: guidance required and, on the other hand, noticeable
cost-reducing effect in large-scale production. I ⁰⁰⁰ parts by weight of polyethylene adipate with a

According to one embodiment according to the invention, average molecular weight of 2000,

the wastes, rejects and / or scrap materials are 16 parts by weight of poly-e-caprolactone diol, mittrialien hot dissolved. This can be done in the way, lower molecular weight 540,

that the appropriately previously usable 13.5 parts by weight of butene-2-diol-1,4,

Pieces of shredded waste, rejects or 17 parts by weight of carbodiimide hydrolysis

First remove old materials in a dry state.

be divided at room temperature. Then 15 ⁴² parts by weight of water, reaction aids, cell

the mixture is heated while stirring and on the regulator and stabilizers,

required solution temperature until io88.5 parts by weight component I,

the polyadducts have dissolved. It is more advantageous processing temperature 55 ° C,

However, the waste to be recycled, scrap parts 469.2 parts by weight 4,4'-diphenylmethane-diiso-

and / or old materials in the already on the solution cyanate waste solution as component II,

temperature preheated, named polyisocyanates, decomposition temperature 35 "C.

to be added in portions and the mixture, too

The cell elastomers obtained in this way are kept at this temperature while stirring

until the introduced polyadducts have dissolved. have the following physical properties:

In both solution methods, the entry of 25 ".. _{,, 3 n 4Q}

Solids expediently in portions and in any- ? % ^ i - "v'i" » «

ger piece size of the parts, preferably about pea tensile strength kp / cm -So

large grain to dusty. Broch elongation, Vo ■ · · · ^4U "

The solution temperature is between 50 and 350 ° C, tear strength, kp / cm 9.5

preferably between 100 and 250 ° C, in special 30 Moßelastizitat, / ₀ ................ ^

Cases also below 50 and above 350 ^° C. Compression set, at RT,% 3.8

After the waste has been dissolved, reject parts Example 2

and / or waste materials are the solutions thus obtained as starting components, the optionally 250 parts by weight of coarse waste from a in addition, those in the waste, scrap parts and / 35 in a one-step operation in the casting process or waste materials containing insoluble substances Polyäthylenglyko'.adipat with a molecular weight contain, for the production of new polyadducts according to von 2000, 1,4-butanediol, trimethylolpropane, Corbodem Isocyanate polyaddition processes used, where diimide hydrolysis protection agents and 4,4'-diphenylmebei the polyadducts in all known forms of thane diisocyanate produced massive polyurethane forms and quality settings are made 40 cast elastomers are added in portions under long cans, total stirring to 1000 parts by weight of 4,4'-diphenyl

Using the method of the invention is methane diisocyanate. After a dissolution time of 50Mies also possible to provide the GR softening grooves of the drop has completely reduce aufsentlich at 160 ⁰ C, resulting in a far-reaching dissolved.

Change in the temperature control during the preparation 45 750 parts by weight of this solution, which can be achieved with some polyadducts in the room. For example, temperature liquid remains, the mixture is heated at 50 ⁰ C and added is the solidification point of 4,4'-diphenylmethane them to a prepared, at 120 ⁰ C starting temperature diisocyanate at 38 ⁰ C. The solution consisting of DIE accommodated mixture 1000 parts by weight of Polysem diisocyanate and a cellular polyurethane-ethylene glycol adipate, average molecular weight 2000, stomer, made from a hydroxyl polyester, 50 159 parts by weight of 1,4-butanediol and 1,5 parts by weight of 1,5-naphthylene diisocyanate and water, is added to space carbodiimide hydrolysis protection agents. After the temperature has passed, it is liquid and can thus be poured in the production run of 90 seconds after the addition of the diisocyanate rate in the production of addition polymers in the case of waste solution, which at this point is still room temperature, which makes the liquefied reaction mixture for the purpose of pre-consolidation a complete problem in terms of driving technology great advantage 55 in a preheated to 125 °, on a heating table. (Heating table ^{temperature - also 125 0} C) standing flat

The following examples illustrate the invention. Tub, the layer thickness of the product being approximately

10 mm.

Example 1 After 2 to 3 minutes standing on the heating table

60 one interrupts the reaction prematurely by

250 parts by weight unevenly coarse or fine - the reaction product of the meanwhile solidified Granularly shredded waste is removed from a two-stage heating table and allowed to cool down to room temperature in the casting process made of polyethylene allowed to cool. Then the obtained, glycol adipate with an average molecular weight of waxy Plat-2000 cooled to room temperature, 1,5-naphthylene diisocyanate, water and some 65 th in airtight and moisture-tight containers and Cellular polyurethane produced by reaction aids allows them to stand for 3 days at room temperature. To elastomers are added in portions with slow storage, the product is granulated and stored Stir to 1000 parts by weight of 4,4'-diphenylmethane for another 2 to 3 days in air and moisture

tight containers. Following this treatment, the product can be further processed thermoplastically. The granules produced in this way, processed by injection molding, give molded articles with the following physical properties Characteristics:

Density, g / cm ³ 1.26

Tensile strength, kp / cm ² 520

Elongation at break 510

Tear strength, kp / cm 81

Abrasion, mm ³ 48

Hardness, Shore A 91

Example 3

250 parts by weight of fine-grained comminuted waste (diameter <0.1 mm) from a two-stage pouring method made of polyethylene glycol adipate, average molecular weight 2000,1,4-butanediol, activated or delayed, trimethylolpropane, carbodiimide hydrolysis protection agent and 1,5-naphthylene-di Solid polyurethane elastomers produced isocyanate are added in portions to 1000 parts by weight of 4,4'-diphenylmethane diisocyanate with slow stirring. After a solution life of 50 minutes at 16O ⁰ C, the waste is completely dissolved.

The solution, which remains liquid at room temperature, is processed further as described in Example 2. The injection molding elastomers obtained in this way have the following physical properties:

Density, g / cm ³ 1.24

Hardness, Shore A 89

Tensile strength, kp / cm ² > 500

Elongation at break,% 460

Tear resistance, kp / cm 67

Abrasion, mm ⁸ 38

Claims (2)

1 2 Waste material that is either in the form of flakes, claims: chips or strips or has been converted into these forms, for filling cushions, impact 1. Process for the recycling of waste, bags, dolls' bodies or similar articles weft parts and / or used materials from Poiyadduk- 5, or these flakes, schnitzel or th, which according to the well-known isocyanate-polyaddi-strips by elastic gluing in molded parts, tion process by implementing organic z. B. mats to transfer. Polyisocyanates or polyisothiocyanates are also known to post hard foam waste organic, at least two active hydrogen comminution as fillers for Atoms-containing compounds in the presence of lean foams or as an additive in the manufacture Usual chain extenders, catalysts, ventilation of lightweight concrete to be used. The crushed ones Accelerated and other common additives hard foam waste are also considered beneficial have been produced, marked by means of soil improvement, draws that from the polyadducts it is also known to waste from thermo- existing waste ^ rejects and / or old plastic processable polyurethanes, given materials in 4,4'-, 2,4'- and / or 2,2'-DiphenyI- falls after appropriate comminution, with fresh methane diisocyanate or a mixture of the! so granules and then continue as usual meren solves. to process. 2. Use of the obtained according to claim 1, it is also known to degrade polyurethane waste, with solutions as reaction components in the 20 for example of polyurethane casting elastomers, thermally carrying out isocyanate polyaddition processes at 180 to 200 ⁰ C and drive the corresponding. Plastic degradation product as a basic product that can be rolled re-use by placing it on the mixing roller work alone or with other commercially available rolling 25 baren starting material blended with an isocyanate blended and networked with the supply of heat. The isocyanate polyaddition process from the German patent specification 962 649 is known In recent years, the polyadducts produced have always been wasted in the production of polyurethane gained more importance. Foams made from polyesters and diisocyanates are particularly common this applies to objects made of polyurethanes, which arise in the presence of water and activators, in constantly increasing amounts are required. Dissolve polyesters or diisocyanates and obtain them With this development, the prototype occurs in turn to soft elastic polyblem on what to process with in making these urethane foams. In the said Polyadducts incurred waste and scrap patent specification, however, is not disclosed which parts as well as the old materials from these Poiyadduk- 35 isocyanates in detail as solvents in beets should do. Waste and rejects arise in all tricks. common by the manufacturing, processing and processing because at the time of registration to the aforementioned processing techniques, when starting up and operating the patent exclusively toluene diisocyanate for Production facilities, which were known to be used in the assembly of the manufacture of foams, must be connected to in storage and transport, in the case of test 40, that only this diisocyanate is taken as Implementations, during testing and commissioning - Solvents used for the foam waste would take from newly built production facilities and not was. Finally, also due to excessively high demands on. In contrast to this, the object of the invention is the weight and dimensional accuracy of the finished parts. do not stop at the recycling of foam - Waste materials are understood to mean products, 45 are limited to falling from polyesterols, but can be used up in practical use through natural, cellular and thermoplastic polyurethanes from wear and tear and through new mate- polyols such as polyesterols, Polycaprolactones and rials have been replaced. Polyetherols, diisocyanates, such as polyphenyl-poly-The wealth of possible variations offered by the methylene-polyisocyanate and hexamethylene-isocyanate-isocyanate polyaddition process allows polysonate and, if necessary, chain-lengthening adducts of the most varied of manifestations and additives dissolved and according to different structures and the individual Forms of appearance, for example the one shot or prepolymer, in turn, in the most varied of quality settings, to produce polyurethanes with the most varied. From each of these manifestations and physical properties are processed.
According to the invention, it has surprisingly been found that the recyclable waste, scrap parts and waste materials come from the most varied of polyurethane waste in proportions. For example, they can consist of fibers or moderately low temperatures very quickly in the polar films of linear polyurethanes; or dissolve from soft diphenylmethane diisocyanate. While in the elastic, semi-rigid or hard foams with examples of German patent specification 962 649 Reak a specific weight between 0.1 and 0.8; ^{or 60 tion temperatures from 180 to 270 0} C and reaction from homogeneous or cellular casting, spraying, injection molding times of IV ₂ to 3 hours are mentioned, or centrifugally cast polyurethane elastomers in which the polyurethane waste is in Diphenylmethandiiso hardness settings of homogeneous qualities between cyanate at temperatures of about 160 ⁰ C in 15 to about 15 Shore A and 60 Sho.u .J, wherein with the designation 60 minutes. In this way, a significantly improved spray polyurethane elastomer all with a thermally better space-time yield is obtained. Plastically processed polyurethanes are meant. Furthermore, it is possible by adding the waste. The examples represent only a selection. Polyurethane the softening range of firm release wheels It is known to significantly reduce flexible polyurethane foam ends. woHnro.li dr-h », · ™